Fungicidal mixtures based on benzamideoxime derivatives, benzophenones and on an azole

ABSTRACT

Fungicidal mixtures, comprising as active components 
 
(1) a benzamideoxime derivative of the formula I  
                 
where the substituent and the index may have the following meanings: 
         R is hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy n is 1, 2 or 3, and 
 
(2) a benzophenone of the formula II,  
                 
in which    R 1  is chlorine, methyl, methoxy, acetoxy, pivaloyloxy or hydroxyl;    R 2  is chlorine or methyl;    R 3  is hydrogen, halogen or methyl; and    R 4  is C 1 -C 6 -alkyl or benzyl, where the phenyl moiety of the benzyl radical may carry a halogen or methyl substituent, and 
 
(3) epoxiconazole of the formula III  
                 
and, if appropriate, 
 
(4) pyraclostrobin of the formula IV  
                 
in a synergistically effective amount are described.

The present invention relates to fungicidal mixtures, comprising asactive components

-   -   (1) a benzamideoxime derivative of the formula I    -   where the substituent and the index may have the following        meanings:    -   R is hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,        C₁-C₄-alkoxy or C₁-C₄-haloalkoxy    -   n is 1, 2 or 3,    -   and    -   (2) a benzophenone of the formula II,        -   in which        -   R¹ is chlorine, methyl, methoxy, acetoxy, pivaloyloxy or            hydroxyl;        -   R² is chlorine or methyl;        -   R³ is hydrogen, halogen or methyl; and        -   R⁴ is C₁-C₆-alkyl or benzyl, where the phenyl moiety of the            benzyl radical may carry a halogen or methyl substituent,            and    -   (3) epoxiconazole of the formula III    -   and, if appropriate,    -   (4) pyraclostrobin of the formula IV    -   in a synergistically effective amount.

Moreover, the invention relates to a method for controlling harmfulfungi using mixtures of the compounds I, II, III and, if appropriate,IV, and to the use of the compounds I, II, III and, if appropriate, IVfor preparing such mixtures, and to compositions comprising thesemixtures.

Benzamideoxime derivatives of the formula I are known from EP-A-1017670.

Fungicidal mixtures comprising, as active compound component, an azole,are known from EP-B 531,837, EP-A 645,091 and WO 97/06678.

The compounds of the formula II, their preparation and their actionagainst harmful fungi are known from the literature (EP-A 727 141; EP-A897 904; EP-A 899 255; EP-A 967 196).

Mixtures of benzophenones of the formula II with other fungicidallyactive compounds are known from EP-A 1 023 834.

Epoxiconazole of the formula III, its preparation and its action againstharmful fungi are known per se from EP-A 196038.

Pyraclostrobin of the formula IV is known from EP-A 0 804 421.

It is an object of the present invention to provide further compositionsfor controlling harmful fungi and in particular for certain indications.

We have found that this object is achieved, surprisingly, by a mixturewhich comprises, as active compounds, benzamideoxime derivatives of theformula I defined at the outset and, as further fungicidally activecomponents, a fungicidally active compound from the class of thebenzophenones, azoles, and, if appropriate, strobilurins.

The mixtures according to the invention act synergistically and aretherefore particularly suitable for controlling harmful fungi and inparticular powdery mildew fungi in cereals, vegetables and grapevines.

In the context of the present invention, halogen denotes fluorine,chlorine, bromine and iodine, and in particular fluorine, chlorine andbromine.

The term “alkyl” includes straight-chain and branched alkyl groups.These are preferably straight-chain or branched C₁-C₄-alkyl groups.Examples of alkyl groups are alkyl such as, in particular, methyl,ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and1,1-dimethylethyl.

Haloalkyl denotes an alkyl group as defined above which is partially orfully halogenated by one or more halogen atoms, in particular byfluorine and chlorine. Preferably, 1 to 3 halogen atoms are present, andparticular preference is given to the difluoromethyl and thetrifluoromethyl groups.

What was said above for the alkyl group and haloalkyl group appliescorrespondingly to the alkyl and haloalkyl groups in alkoxy andhaloalkoxy.

The radical R in the formula I preferably is a hydrogen atom.

The following compounds of the formula II are preferred mixing partners,the individual preferences applying on their own or in combination.

Preference is given to compounds II in which R¹ is chlorine, methoxy,acetoxy or hydroxyl, and particular preference is given to compounds inwhich R¹ is methoxy, acetoxy or hydroxyl. Very particular preference isgiven to compounds in which R¹ is methoxy.

Mixtures according to the invention comprise compounds II in which R² ischlorine or methyl. Preference is given to compounds II in which R² ismethyl.

Moreover, preference is given to compounds II in which R³ is hydrogen,methyl, chlorine or bromine and with particular preference hydrogen,chlorine or bromine.

In addition, preference is given to compounds II in which R⁴ isC₁-C₄-alkyl or benzyl, where the phenyl moiety of the benzyl radical maycarry a halogen or methyl substituent. Particularly preferred arecompounds of the formula II in which R⁴ is C₁-C₄-alkyl, preferablymethyl.

Preference is furthermore given to compounds of the formula II in whichthe substituents R¹, R², R³ and R⁴ are as defined below:

-   -   R¹ is methoxy, acetoxy or hydroxyl;    -   R² is methyl;    -   R³ is hydrogen, chlorine or bromine; and    -   R⁴ is C₁-C₄-alkyl.

Additionally, particular preference is given to compounds of the formulaII in which the substituents have the meanings given in table 1 below:II

No. R¹ R² R³ R⁴ II-1 methoxy Cl H methyl II-2 methoxy Cl methyl methylII-3 methoxy Cl H n-propyl II-4 methoxy Cl H n-butyl II-5 methoxy Cl Hbenzyl II-6 methoxy Cl H 2-fluorobenzyl II-7 methoxy Cl H 3-fluorobenzylII-8 methoxy Cl H 4-fluorophenyl II-9 methoxy Cl H 2-methylphenyl II-10methoxy Cl H 3-methylphenyl II-11 methoxy Cl H 4-methylphenyl II-12methoxy Cl Br methyl II-13 methoxy Cl Br n-propyl II-14 methoxy Cl Brn-butyl II-15 methoxy Cl Br benzyl II-16 methoxy Cl Br 2-fluorobenzylII-17 methoxy methyl H methyl II-18 methoxy methyl Cl methyl II-19methoxy methyl H n-propyl II-20 methoxy methyl H n-butyl II-21 methoxymethyl H benzyl II-22 methoxy methyl H 2-fluorobenzyl II-23 methoxymethyl H 3-fluorobenzyl II-24 methoxy methyl H 4-fluorophenyl II-25methoxy methyl H 2-methylphenyl II-26 methoxy methyl H 3-methylphenylII-27 methoxy methyl H 4-methylphenyl II-28 methoxy methyl Br methylII-29 methoxy methyl Br n-propyl II-30 methoxy methyl Br n-butyl II-31methoxy methyl Br benzyl II-32 methoxy methyl Br 2-fluorobenzyl II-33acetoxy methyl H methyl II-34 acetoxy methyl Cl methyl II-35 acetoxymethyl Br methyl II-36 hydroxy methyl H methyl II-37 hydroxy methyl Clmethyl II-38 hydroxy methyl Br methyl II-39 pivaloyloxy methyl H methylII-40 pivaloyloxy methyl Cl methyl II-41 pivaloyloxy methyl Br methylII-42 Cl Cl H methyl II-43 Cl Cl H n-propyl II-44 Cl Cl H n-butyl II-45Cl Cl H benzyl II-46 Cl Cl H 2-fluorobenzyl II-47 Cl Cl H 3-fluorobenzylII-48 Cl Cl H 4-fluorophenyl II-49 Cl Cl H 2-methylphenyl II-50 Cl Cl H3-methylphenyl II-51 Cl Cl H 4-methylphenyl II-52 Cl Cl Br methyl II-53Cl Cl Br n-propyl II-54 Cl Cl Br n-butyl II-55 Cl Cl Br benzyl II-56 ClCl Br 2-fluorobenzyl II-57 methyl methyl H methyl II-58 methyl methyl Hn-propyl II-59 methyl methyl H n-butyl II-60 methyl methyl H benzylII-61 methyl methyl H 2-fluorobenzyl II-62 methyl methyl H3-fluorobenzyl II-63 methyl methyl H 4-fluorophenyl II-64 methyl methylH 2-methylphenyl II-65 methyl methyl H 3-methylphenyl II-66 methylmethyl H 4-methylphenyl II-67 methyl methyl Br methyl II-68 methylmethyl Br n-propyl II-69 methyl methyl Br n-butyl II-70 methyl methyl Brbenzyl II-71 methyl methyl Br 2-fluorobenzyl

The azole derivative in the mixtures according to the invention isepoxiconazole of the formula III. The mixtures according to theinvention may additionally comprise pyraclostrobin of the formula IV.

For the synergistic action to unfold, even a small proportion ofbenzamideoxime derivative of the formula I is sufficient. Preferably,benzamideoxime derivative, benzophenone and epoxiconazole are employedin a weight ratio in the range from 20:1:1 to 1:20:20, in particularfrom 10:1:1 to 1:10:10.

Owing to the basic character of its nitrogen atoms, epoxiconazole of theformula III is capable of forming salts or adducts with inorganic ororganic acids or with metal ions.

Examples of inorganic acids are hydrohalic acids, such as hydrogenfluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide,carbonic acid, sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, and alkanoicacids, such as acetic acid, trifluoroacetic acid, trichloroacetic acidand propionic acid, and also glycolic acid, thiocyanic acid, lacticacid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalicacid, alkylsulfonic acids (sulfonic acids having straight-chain orbranched alkyl radicals with 1 to 20 carbon atoms), arylsulfonic acidsor aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl,which carry one or two sulfo groups), alkylphosphonic acids (phosphonicacids having straight-chain or branched alkyl radicals with 1 to 20carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromaticradicals, such as phenyl and naphthyl, which carry one or two phosphonicacid radicals)., it being possible for the alkyl or aryl radicals tocarry further substituents, for example p-toluenesulfonic acid,salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid,2-acetoxybenzoic acid, etc.

Suitable metal ions are, in particular, the ions of the elements of thefirst to eighth transition groups, especially chromium, manganese, iron,cobalt, nickel, copper, zinc, and additionally those of the second maingroup, especially calcium and magnesium, and of the third and fourthmain groups, in particular aluminum, tin and lead. If appropriate, themetals can be present in the various valences which they can assume.

If pyraclostrobin IV is employed, too, benzamideoxime derivative I,benzophenone II, epoxiconazole III and pyraclostrobin IV are employed ina weight ratio of from 20:1:1:1 to 1:20:20:20, preferably from 10:1:1:1to 1:10:10:10.

When preparing the mixtures, it is preferred to employ the pure activecompounds I to III and, if appropriate, IV, with which further activecompounds against harmful fungi or other pests, such as insects,arachnids or nematodes, or else herbicidal or growth-regulating activecompounds or fertilizers can be admixed.

The mixtures of the compounds I, II and III and, if appropriate, IV, orthe simultaneous joint or separate use of the compounds I, II and IIIand, if appropriate, IV, have outstanding action against a wide range ofphytopathogenic fungi, in particular from the classes of theAscomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. Some ofthem act systemically and are therefore also suitable for use as foliar-and soil-acting fungicides.

They are especially important for controlling a large number of fungi ina variety of crop plants, such as cotton, vegetable species (for examplecucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass,oats, bananas, coffee, corn, fruit species, rice, rye, soya, grapevine,wheat, ornamentals, sugarcane, and a variety of seeds.

They are particularly suitable for controlling the followingphytopathogenic fungi: Blumeria graminis (powdery mildew) in cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,Podosphaera leucotricha in apples, Uncinula necator in grapevines,Puccinia species in cereals, Rhizoctonia species in cotton, rice andlawns, Ustilago species in cereals and sugarcane, Venturia inaequalis(scab) in apples, Helminthosporium species in cereals, Septoria nodorumin wheat, Botrytis cinera (gray mold) in strawberries, vegetables,ornamentals and grapevines, Cercospora arachidicola in ground nuts,Pseudocercosporella herpotrichoides in wheat and barley, Pyriculariaoryzae in rice, Phytophthora infestans in potatoes and tomatoes,Plasmopara viticola in grapevines, Pseudoperonospora species in hops andcucumbers, Alternaria species in vegetables and fruit, Mycosphaerellaspecies in bananas and Fusarium and Verticillium species.

The mixtures according to the invention are particularly preferably usedfor controlling powdery mildew fungi in crops of cereals, grapevines andvegetables,, and also in ornamentals.

Compounds I, II, III and, if appropriate, IV can be appliedsimultaneously, that is either together or separately, or in succession,the sequence, in the case of separate application, generally not havingany effect on the control results.

Depending on the desired effect, the application rates of the mixturesaccording to the invention are, in particular on areas underagricultural cultivation, from 0.01 to 8 kg/ha, preferably from 0.1 to 5kg/ha, in particular from 0.5 to 3.0 kg/ha..

For the compounds I, the application rates are from 0.01. to 2.5 kg/ha,preferably from 0.05 to 2.5 kg/ha, in, particular from 0.1 to 1.0 kg/ha.

Correspondingly, the application rates for the compounds II and III and,if appropriate, IV are from 0.01 to 10 kg/ha, preferably from 0.05 to 5kg/ha, in particular from 0.05 to 2.0 kg/ha.

For seed treatment, the application rates of the mixture are generallyfrom 0.001 to 250 g/kg of seed, preferably from 0.01 to 100 g/kg, inparticular from 0.01 to 50 g/kg.

If phytopathogenic harmful fungi are to be controlled, the separate orjoint application of the compounds I, II, III and, if appropriate, IV orof the mixtures of the compounds I, II, III and, if appropriate, IV iseffected by spraying or dusting the seeds, the plants or the soilsbefore or after sowing of the plants, or before or after plantemergence.

The fungicidal synergistic mixtures according to the invention, or thecompounds I, II, III and, if appropriate, IV, can be formulated, forexample, in the form of ready-to-spray solutions, powders andsuspensions or in the form of highly concentrated aqueous, oily or othersuspensions, dispersions, emulsions, oil dispersions, pastes, dusts,materials for broadcasting or granules, and applied by spraying,atomizing, dusting, broadcasting or watering. The use form depends onthe intended purpose; in each case, it should ensure as fine and uniforma distribution as possible of the mixture according to the invention.

The formulations are prepared in a known manner, for example byextending the active compound with solvents and/or carriers, if desiredusing emulsifiers and dispersants, where, if the diluent used is water,it is also possible to use other, organic solvents as auxiliarysolvents. Auxiliaries suitable for this purpose are essentially:solvents such as aromatic compounds (for example xylene), chlorinatedaromatic compounds (for example chlorobenzenes), paraffins (for examplemineral oil fractions), alcohols (for example methanol, butanol),ketones (for example cyclohexanone), amines (for example ethanolamine,dimethylformamide) and water; carriers, such as ground natural minerals(for example kaolins, clays, talc, chalk) and ground synthetic minerals(for example finely divided silica, silicates); emulsifiers, such asnonionic and anionic emulsifiers (for example polyoxyethylene fattyalcohol ethers, alkylsulfonates and arylsulfonates) and dispersants,such as lignosulfite waste liquors and methylcellulose.

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts and ammonium salts of aromatic sulfonic acids, for example ligno-,phenol-, naphthalene- and dibutylnaphthalenesulfonic acids, and of fattyacids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fattyalcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols,or of fatty alcohol glycol ethers, condensates of sulfonated naphthaleneand its derivatives with formaldehyde, condensates of naphthalene or ofthe naphthalenesulfonic acids with phenol and formaldehyde,polyoxyethylene octylphenyl ether, ethoxylated isooctyl-, octyl- ornonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycolethers, alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, laurylalcohol polyglycol ether acetate, sorbitol esters, lignosulfite wasteliquors or methylcellulose.

Powders, materials for broadcasting and dusts can be prepared by mixingor jointly grinding the compounds I, II, III and, if appropriate, IV, orthe mixture of the compounds I, II, III and, if appropriate, IV with asolid carrier.

Granules (for example coated granules, impregnated granules orhomogeneous granules) are usually prepared by binding the activecompound, or the active compounds, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths, such assilica gel, silicic acids, silicates, talc, kaolin, limestone, lime,chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials, andfertilizers, such as ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas and products of vegetable origin, such as cereal meal,tree bark meal, wood meal and nutshell meal, cellulose powders or othersolid carriers.

The formulations generally comprise from 0.1 to 95% by weight,preferably from 0.5 to 90% by weight, of one of the compounds I, II orIII or, if appropriate, IV, or of the mixture of the compounds I, II andIII and, if appropriate, IV. The active compounds are employed in apurity of from 90% to 100%, preferably from 95% to 100% (according toNMR spectrum or HPLC).

The compounds I, II, III or, if appropriate, IV, the mixtures or thecorresponding formulations are applied by treating the harmful fungi,their habitat, or the plants, seeds, soils, areas, materials or spacesto be kept free from them with a fungicidally effective amount of themixture, or of the compounds I, II and III and, if appropriate, IV, inthe case of separate application.

Application can be effected before or after infection by the harmfulfungi.

Examples of such preparations comprising the active compounds are:

-   -   I. a solution of 90 parts by weight of the active compounds and        10 parts by weight of N-methylpyrrolidone which is suitable for        use in the form of microdrops;    -   II. a mixture of 20 parts by weight of the active compounds, 80        parts by weight of xylene, 10 parts by weight of the adduct of 8        to 10 mol of ethylene oxide to 1 mol of oleic acid        N-monoethanolamide, 5 parts by weight of calcium        dodecylbenzenesulfonate, 5 parts by weight of the adduct of 40        mol of ethylene oxide to 1 mol of castor oil; a dispersion is        obtained by finely distributing the solution in water.    -   III. an aqueous dispersion of 20 parts by weight of the active        compounds, 40 parts by weight of cyclohexanone, 30 parts by        weight of isobutanol, 20 parts by weight of the adduct of 40 mol        of ethylene oxide to 1 mol of castor oil;    -   IV. an aqueous dispersion of 20 parts by weight of the active        compounds, 25 parts by weight of cyclohexanol, 65 parts by        weight of a mineral oil fraction of boiling point 210 to 280° C.        and 10 parts by weight of the adduct of 40 mol of ethylene oxide        to 1 mol of castor oil;    -   V. a mixture, ground in a hammer mill, of 80 parts by weight of        the active compounds, 3 parts by weight of sodium        diisobutylnaphthalene-1-sulfonate, 10 parts by weight of a        sodium lignosulfonate from a sulfite waste liquor and 7 parts by        weight of pulverulent silica gel; a spray mixture is obtained by        finely distributing the mixture in water;    -   VI. an intimate mixture of 3 parts by weight of the active        compounds and 97 parts by weight of finely divided kaolin; this        dust comprises 3% by weight of active compound;    -   VII. an intimate mixture of 30 parts by weight of the active        compounds, 92 parts by weight of pulverulent silica gel and 8        parts by weight of paraffin oil which has been sprayed onto the        surface of this silica gel; this preparation imparts good        adhesion properties to the active compound;    -   VIII. a stable aqueous dispersion of 40 parts by weight of the        active compounds, 10 parts by weight of the sodium salt of a        phenolsulfonic acid/urea/formaldehyde condensate, 2 parts by        weight of silica gel and 48 parts by weight of water, which can        be diluted further;    -   IX. a stable oily dispersion of 20 parts by weight of the active        compounds, 2 parts by weight of calcium dodecylbenzenesulfonate,        8 parts by weight of fatty alcohol polyglycol ether, 20 parts by        weight of the sodium salt of a phenolsulfonic        acid/urea/formaldehyde condensate and 88 parts by weight of a        paraffinic mineral oil.

USE EXAMPLE

The synergistic action of the mixtures according to the invention can bedemonstrated by the following experiments:

The active compounds are prepared separately or together as a 10%strength emulsion in a mixture of 63% by weight of cyclohexanone and 27%by weight of emulsifier and diluted with water to the desiredconcentration.

Evaluation is carried out by determining the infected leaf areas inpercent. These percentages are converted into efficacies. The efficacy(E) is calculated as follows using Abbot's formula:E=(1−α)*100/β

-   -   α corresponds to the fungal infection of the treated plants in %        and    -   β corresponds to the fungal infection of the untreated (control)        plants in %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants were not infected.

The expected efficacies of the active compound mixtures were determinedusing Colby's formula [S. R. Colby, Weeds 15, 20-22 (1967)] and comparedwith the observed efficacies.Colby's formula: E=x+y−x−y/100

-   -   E expected efficacy, expressed in % of the untreated control,        when using the mixture of the active compounds A and B at the        concentrations a and b    -   x efficacy, expressed in % of the untreated control, when using        active compound A at a concentration of a    -   y efficacy, expressed in % of.the untreated control, when using        active compound B at a concentration of b

Use Example 1 Activity Against Mildew of Wheat Caused by Erysiphe [syn.Blumeria] graminis Forma Specialis tritici

Leaves of potted wheat seedlings of the cultivar “Kanzler” were sprayedto runoff point with an aqueous suspension having the concentration ofactive compound stated below. The suspension or emulsion had beenprepared from a stock solution comprising 10% of active compound in amixture consisting of 85% of cyclohexanone and 5% of emulsifier. 24hours after the spray coating had dried on, the seedlings were dustedwith spores of mildew of wheat (Erysiphe [syn. Blumeria] graminis formaspecialis tritici). The test plants were then placed in a greenhouse attemperatures between 20 and 24° C. and 60 to 90% relative atmospherichumidity. After 7 days, the extent of the mildew development wasdetermined visually in % infection of the total leaf area.

The visually determined percentages of infected leaf area were convertedinto efficacies as % of the untreated control. An efficacy of 0 meansthe infection level of the treated plants corresponds to that of theuntreated control; an efficacy of 100 means 0% infection. The expectedefficacies of the combinations of active compounds were determined usingColby's formula (Colby, S. R. “Calculating synergistic and antagonisticresponses of herbicide Combinations”, Weeds, 15, pp., 20-22, 1967) andcompared with the observed efficacies. TABLE 2 Concentration of activecompound in Efficacy in % of the spray liquor the untreated Activecompound in ppm control Control (untreated) (90% infection) 0 Compound Iwhere R_(n) = H 0.25 56 0.06 33 Compound II = metrafenone = 1 72 whereR¹ = OCH₃, 0.25 56 R² = CH₃, R³ = Br, R⁴ = CH₃ 0.06 44 0.015 33 CompoundIII = epoxiconazole 1 56 0.25 44 0.06 33 0.015 0 Compound IV =pyraclostrobin 1 33 0.25 0 0.06 0 0.015 0

TABLE 3 Two-component combination from Observed Calculated EP 1 023 834efficacy efficacy*) Compound II = metrafenone + 83 80 compound III =epoxiconazole 0.25 + 1 ppm mixture 1:4 Compound II = metrafenone + 78 69compound III = epoxiconazole 0.06 + 0.25 ppm mixture 1:4 Compound II =metrafenone + 72 70 compound III = epoxiconazole 0.25 + 0.06 ppm mixture4:1 Compound II = metrafenone + 67 44 compound III = epoxiconazole0.06 + 0.015 ppm mixture 4:1

TABLE 4 Two-component combination from Observed Calculated WO 02/062140efficacy efficacy*) Compound I where R_(n) = H + 78 75 compound II =metrafenone 0.25 + 0.06 ppm mixture 4:1 Compound I = where R_(n) = H +67 56 compound II = metrafenone 0.06 + 0.015 ppm mixture 4:1 Compound I= where R_(n) = H + 89 88 compound II = metrafenone 0.25 + 1 ppm mixture1:4 Compound I = where R_(n) = H + 72 70 compound II = metrafenone0.06 + 0.25 ppm mixture 1:4

TABLE 5 Two-component combination from Observed Calculated WO 02/056686efficacy efficacy*) Compound II = metrafenone + 78 70 compound IV =pyraclostrobin 0.25 + 1 ppm mixture 1:4 Compound II = metrafenone + 5644 compound IV = pyraclostrobin 0.06 + 0.25 ppm mixture 1:4 Compound II= metrafenone + 78 56 compound IV = pyraclostrobin 0.25 + 0.06 ppmmixture 4:1 Compound II = metrafenone + 72 44 compound IV =pyraclostrobin 0.06 + 0.015 ppm mixture 4:1

TABLE 6 Three-component combinations Observed Calculated claimedefficacy efficacy*) Compound I where R_(n) = H + compound 100 93 II =metrafenone + compound III = epoxiconazole from EP 1 023 834) 0.25 +0.25 + 1 ppm mixture 1:1:4 Compound I where R_(n) = H + compound 97 85II = metrafenone + compound III = epoxiconazole 0.06 + 0.06 + 0.25 ppmmixture 1:1:4 Compound I where R_(n) = H + compound 97 88 II =metrafenone + compound III = epoxiconazole 0.25 + 0.25 + 0.06 ppmmixture 4:4:1 Compound I where R_(n) = H + compound 94 78 II =metrafenone + compound III = epoxiconazole 0.06 + 0.06 + 0.015 ppmmixture 4:4:1 Compound I where R_(n) = H + compound 97 88 II =metrafenone + compound III = epoxiconazole 0.25 + 0.06 + 0.25 ppmmixture 4:1:4 Compound I where R_(n) = H + compound 87 78 II =metrafenone + compound III = epoxiconazole 0.06 + 0.015 + 0.06 ppmmixture 4:1:4 Compound I where R_(n) = H + compound 97 94 II =metrafenone + compound III = epoxiconazole 0.25 + 1 + 0.25 ppm mixture1:4:1 Compound I where R_(n) = H + compound 94 81 II = metrafenone +compound III = epoxiconazole 0.06 + 0.25 + 0.06 ppm mixture 1:4:1Compound I where R_(n) = H + compound 94 78 II = metrafenone + compoundIV = pyraclostrobin 0.25 + 0.06 + 0.25 ppm mixture 4:1:4 Compound Iwhere R_(n) = H + compound 78 67 II = metrafenone + compound IV =pyraclostrobin 0.06 + 0.015 + 0.06 ppm mixture 4:1:4 Compound I whereR_(n) = H + compound 100 89 II = metrafenone + compound IV =pyraclostrobin 0.25 + 1 + 0.25 ppm mixture 1:4:1 Compound I where R_(n)= H + compound 83 72 II = metrafenone + compound IV = pyraclostrobin0.06 + 0.25 + 0.06 ppm mixture 1:4:1 Compound I where R_(n) = H +compound 99 90 II = metrafenone + compound IV = pyraclostrobin 0.25 +0.25 + 1 ppm mixture 1:1:4 Compound I where R_(n) = H + compound 83 70II metrafenone + compound IV = pyraclostrobin 0.06 + 0.06 + 0.25 ppmmixture 1:1:4 Compound I where R_(n) = H + compound 100 90 II =metrafenone + compound IV = pyraclostrobin 0.25 + 0.25 + 0.06 ppmmixture 4:4:1 Compound I where R_(n) = H + compound 94 81 II =metrafenone + compound IV = pyraclostrobin 0.06 + 0.06 + 0.015 ppmmixture 4:4:1

Use Example 2 Curative Activity Against Brown Rust of Wheat Caused byPuccinia recondita

Curative Activity Against Brown Rust of Wheat Caused by Pucciniarecondita

Leaves of potted wheat seedlings of the cultivar “Kanzler” were dustedwith spores of brown rust (Puccinia recondita). The pots were thenplaced in a chamber with high atmospheric humidity (90 to 95%), at 20 to22° C., for 24 hours. During this period of time, the spores germinatedand the germinal tubes penetrated into the leaf tissue. The next day,the infected plants were sprayed to runoff point with an aqueoussuspension having the concentration of active compound stated below. Thesuspension or emulsion had been prepared from a stock solutioncomprising 10% of active compound in a mixture consisting of 85% ofcyclohexanone and 5% of emulsifier. After the spray coating had driedon, the test plants were cultivated in a greenhouse at temperaturesbetween 20 and 22° C. and at 65 to 70% relative atmospheric humidity for7 days. The extent of the rust fungus development on the leaves was thendetermined.

The visually determined percentages of infected leaf areas wereconverted into efficacies as % of the untreated control. An efficacy of0 means that the infection level of the treated plants corresponds tothat of the untreated control; an efficacy of 100 means 0% infection.The expected efficacies of the combinations of active compounds weredetermined using Colby's formula (Colby, S. R. “Calculating synergisticand antagonistic responses of herbicide Combinations”, Weeds, 15, pp.20-22, 1967) and compared with the observed efficacies. TABLE 7Concentration of Efficacy active compound in % of in the spray theuntreated Active compound liquor in ppm control Control (untreated) (90%infection) 0 Compound I where Rn = H 0.25 0 0.06 0 Compound II =metrafenone = where 1 0 R¹ = OCH₃, R² = CH₃, R³ = Br, 0.25 0 R⁴ = CH₃0.06 0 0.015 0 Compound III = epoxiconazole 1 94 0.25 89 0.06 67 0.015 0Compound IV = pyraclostrobin 1 78 0.25 33 0.06 33 0.015 22

TABLE 8 Two-component combination from Observed Calculated EP 1 023 834efficacy efficacy*) Compound II = metrafenone + 97 94 compound III =epoxiconazole 0.25 + 1 ppm mixture 1:4 Compound II = metrafenone + 94 89compound III = epoxiconazole 0.06 + 0.25 ppm mixture 1:4 Compound II =metrafenone + 83 67 compound III = epoxiconazole 0.25 + 0.06 ppm mixture4:1 Compound II = metrafenone + 33 0 compound III = epoxiconazole 0.06 +0.015 ppm mixture 4:1

TABLE 9 Two-component combination from Observed Calculated WO 02/062140efficacy efficacy*) Compound I = where R_(n) = H + 0 0 compound II =metrafenone 0.25 + 0.06 ppm mixture 4:1 Compound I = where R_(n) = H + 00 compound II = metrafenone 0.06 + 0.015 ppm mixture 4:1 Compound I =where R_(n) = H + 0 0 compound II = metrafenone 0.25 + 1 ppm mixture 1:4Compound I = where R_(n) = H + 0 0 compound II = metrafenone 0.06 + 0.25ppm mixture 1:4

TABLE 10 Two-component combination from Observed Calculated WO 02/056686efficacy efficacy*) Compound II = metrafenone + 89 78 compound IV =pyraclostrobin 0.25 + 1 ppm mixture 1:4 Compound II = metrafenone + 5633 compound IV = pyraclostrobin 0.06 + 0.25 ppm mixture 1:4 Compound II= metrafenone + 56 33 compound IV = pyraclostrobin 0.25 + 0.06 ppmmixture 4:1 Compound II = metrafenone + 44 22 compound IV =pyraclostrobin 0.06 + 0.015 ppm mixture 4:1

TABLE 11 Three-component combinations Observed Calculated claimedefficacy efficacy*) Compound I where R_(n) = H + compound 100 97 II =metrafenone + compound III = epoxiconazole 0.25 + 0.25 + 1 ppm mixture1:1:4 Compound I where R_(n) = H + compound 100 94 II = metrafenone +compound III = epoxiconazole 0.06 + 0.06 + 0.25 ppm mixture 1:1:4Compound I where R_(n) = H + compound 94 83 II = metrafenone + compoundIII = epoxiconazole 0.25 + 0.25 + 0.06 ppm mixture 4:4:1 Compound Iwhere R_(n) = H + compound 56 33 II = metrafenone + compound III =epoxiconazole 0.06 + 0.06 + 0.015 ppm mixture 4:4:1 Compound I whereR_(n) = H + compound 100 89 II = metrafenone + compound III =epoxiconazole 0.25 + 0.06 + 0.25 ppm mixture 4:1:4 Compound I whereR_(n) = H + compound 83 67 II = metrafenone + compound III =epoxiconazole 0.06 + 0.015 + 0.06 ppm mixture 4:1:4 Compound I whereR_(n) = H + compound 100 89 II = metrafenone + compound III =epoxiconazole 0.25 + 1 + 0.25 ppm mixture 1:4:1 Compound I where R_(n) =H + compound 78 67 II = metrafenone + compound III = epoxiconazole0.06 + 0.25 + 0.06 ppm mixture 1:4:1 Compound I where R_(n) = H +compound 56 33 II = metrafenone + compound IV = pyraclostrobin 0.25 +0.06 + 0.25 ppm mixture 4:1:4 Compound I where R_(n) = H + compound 4433 II = metrafenone + compound IV = pyraclostrobin 0.06 + 0.015 + 0.06ppm mixture 4:1:4 Compound I where R_(n) = H + compound 67 33 II =metrafenone + compound IV = pyraclostrobin 0.25 + 1 + 0.25 ppm mixture1:4:1 Compound I where R_(n) = H + compound 50 33 II = metrafenone +compound IV = pyraclostrobin 0.06 + 0.25 + 0.06 ppm mixture 1:4:1Compound I where R_(n) = H + compound 97 89 II = metrafenone + compoundIV = pyraclostrobin 0.25 + 0.25 + 1 ppm mixture 1:1:4 Compound I whereR_(n) = H + compound 72 56 II = metrafenone + compound IV =pyraclostrobin 0.06 + 0.06 + 0.25 ppm mixture 1:1:4 Compound I whereR_(n) = H + compound 67 56 II = metrafenone + compound IV =pyraclostrobin 0.25 + 0.25 + 0.06 ppm mixture 4:4:1 Compound I whereR_(n) = H + compound 56 44 II = metrafenone + compound IV =pyraclostrobin 0.06 + 0.06 + 0.015 ppm mixture 4:4:1*)efficacy calculated using Colby's formula

The test results show that for all mixing ratios the observed efficacyis higher than the efficacy predicted using Colby's formula (from Synerg188. XLS).

1. A fungicidal mixture, comprising as active components (1) abenzamideoxime derivative of the formula I.

where the substituent and the index may have the following meanings:. Ris hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy n is 1, 2 or 3, and (2) a benzophenone of the formulaII,

in which R¹ is chlorine, methyl, methoxy, acetoxy, pivaloyloxy orhydroxyl; R² is chlorine or methyl; R³ is hydrogen, halogen or methyl;and R⁴ is C₁-C₆-alkyl or benzyl, where the phenyl moiety of the benzylradical may carry a halogen or methyl substituent, and (3) epoxiconazoleof the formula III

in a synergistically effective amount.
 2. A fungicidal mixture asclaimed in claim 1, furthermore comprising (4) pyraclostrobin of theformula IV


3. A fungicidal mixture as claimed in claim 1, where the radical R inthe formula I is hydrogen.
 4. A fungicidal mixture as claimed in any ofclaims 1 to 3, where in the formula II R¹ is methoxy, acetoxy orhydroxyl, R² is methyl, R³ is hydrogen, chlorine or bromine, and R⁴ isC₁-C₄-alkyl.
 5. A fungicidal mixture as claimed in claim 4, where in theformula II R¹ is methoxy, R², R⁴ are methyl and R³ is bromine;
 6. Afungicidal mixture as claimed in claim 1, where the weight ratio of thebenzamideoxime derivative of the formula I to the benzophenone of theformula II and the epoxiconazole of the formula III is from 20:1:1 to1:20:20.
 7. A method for controlling harmful fungi, which comprisestreating the harmful fungi, their habitat, or the plants, seeds, soils,areas, materials or spaces to be kept free from them with the fungicidalmixture as claimed in claim
 1. 8. A method as claimed in claim 7, whichcomprises applying the compounds of the formulae I, II and III as setforth in claim 1 simultaneously, that is either together or separately,or in succession.
 9. A method as claimed in claim 7 or 8, wherein thefungicidal mixture or the compounds of the formulae I, II and III areapplied in an amount of from 0.01 to 8 kg/ha.
 10. A fungicidalcomposition, comprising the fungicidal mixture as claimed in claim 1 anda solid or liquid carrier.